Calcining finely divided limestone



y 1954 H. w. B EHME ET AL 2,684,840

CALCINING FINELY DIVIDED LIMESTONE Filed April 6, 1951 2 Sheets-Sheet l Fig.

Cu O 'o 0000 /V W BEHME 8 OBE/?T E. THOMPSO/V INVENTOR HE/?MA ATTORNEY July 27, 1 954 w BEHME ET 2,684,840

CALCINING FINELy DIVIDED LIMESTONE Filed April e, 1951 2 sheets sheet 2 I J I:

ATTO R N EY Patentecl July 27, 1954 2,684,840 CALCINING FINELY DIVIDED LIMESTONE 'Hermann W.Behme, Norwalk, and Robert B. Thompson,` Wilton, Com., ass'gnors to The *Dorr Company,

of Delaware Stamford, Conn., a Corporation Application April 6, 1951, Serial No. .219,624

3 Claims. l

This invention relates generally to the calcination of limestone and more particularly to the more eficient calcination of nely divided'limestone in fiuidized solids reactors.

In the calcinaton of limestone employing the fluidized solids technique considerable diiculty is experienceddue to .excessive dust losses. This dust is of two types, (1) limestone dust (CaCO3) formed when the limestone is crushed prior to introduction into the reactor, and (2) calcined lime dust (Cao) which is produced by the decrepitation or breakdown of calcined lime within the calcining 'chamber of the reactor. 'Both types of dust are salable products; the limestone (CaCO3) finds extensive use as "agricultural stone" While the lime (Cao) is valuable as a reactant. However the commercial worth of these 'products is directly dependent upon their purity; that is, 'limestone is of little value unless it is substantially free from calcined lime, and the calcined lime dust is of small worth'u-nless it is substanti'ally'free fromlimestone. Therefore, it is important that the lime dust and the limestone 'dust be recovered'separately from each other.

Heretofore, finely divided limestone-has been i calcined in multi 'chambered fiuidized solids reactors in which one or more superjacent chambers 'are maintained as limestone `preheating chambers 'while one or more subjacent' chambers are maintainedas calcining chambers. In such reactors the lime (Cao) dust is carried from the calcining chamber'entrained in a mixture of fiuidizing gas and' liberatedcoz andsuch gas is passed through a cyclone'or. other dust-diminisher to recover 'such entrainedrlime' dust as substantially pure product. The 'dust-freerhot 'gases are then used to fiuidize' and'preheat incoming limestone solids in the superjacent preheating beds. A major portion `of-the limestone (CaCOs) dust is removed from the finely divided feed before such feedenters the calcining chamber ;this is accomplished eitherby 'classifying the` crushedlimestone to remove the: limestone. dust therefrom before introducing thelimestone into the reactor, or by utilizing one or more 'of'the fluidized solids preheating chambers as a classifying chamber "wherein the lim'estone is entrained n'the fluidizing gas 'passing'through such chamber and is carried out of i the'reactor to separate recovery.

However, such*proc'esses 'although highly successful are nevertheless subject'to severe economic limitations in'aequipment cost and .operation.` These'limitations 'are due mainly to the 'high temperatures atwhich the calcining 'cham- 'ber must be maintainedas Well as to the fact-that the calcining temperatures may be intentionally varied over a considerable range in order to alter the characteristics of the calcined product. The successful calcination of limestcne requires a temperature in the range of 1700 to 1950 F. and this means that the dust-laden gases leaving the calcining chamber are also of that temperature range. Moreover, since the calcining chamber is the hottest part of the reactor the gases exiting from such chamber occupy a relatively large Volume due to heat-induced ex-pansion. Further, whenever the calcining chamber temperature is raised or lowered it results in a raising or lowering of the exit gas temperature as well as in a change in the Volume occupied by such gas and this Volume change affects the efiiciency of the cyclone.

` 'The above factors, high temperature, large gas Volume, and gas temperature and Volume variations require that the cyclone employed to intercept calcining chamber exit gases must be constructed of expensive heat-resistant material and must be of sufiicient size to'handle the largest expectable gas Volume in order that the gas load placed upon such 'cyclone does not seriously impair its eiciency.

So it is one object of this invention to provide ways and means whereby the cyclone employed to recover entrained calcined lime dust from dustladen calcining chamber exit gases' may be operated at a substantially constant lower temperature thus providing a substantially constant smaller gas Volume entering'the cyclone and allowing forthe use of a smaller less expensive cyclone which will operate' at a substanti'ally constant eiciency level.

Broadly stated, this invention proposes to calcine finely divided limestone solids in a fiuidized solids reactor having a pluralityof fiuidized beds including at least two such beds maintained under solids preheating conditions and at least one such bed maintained under solids calcining conditions. Hot lime-'dust-laden gases exiting from the calcining bed are passed upwarcly through at least one solids preheating bed Where such dust-laden gases are conditioned as to temperature and Volume for furtherhandling in a dustdiminishing station, thence to a dust-'diminishing station for recovery of the entrained lime dust after which the dust-free gas is discharged or sent to further use such' as p'eheating le the recovered lime dust is utilized as valuable product.

An important feature of this invention lies in the discovery that the dust-laden gases entering the dust-diminishin station are automatically maintained at a substantially constant temperature and Volume that is significantly lower than the temperature and Volume of such gases as they leave the calcining bed thus rendering the operation of the dust-diminishing station uniformly efiicient. This uniformity of temperature and Volume is due to the discovery that, even though the temperature in the oalcining bed may vary over a considerable range of say 200 F., nevertheless the temperature in the preheating bed through which the calcining chamber dust-laden exit gases pass will remain at a substantially constant but signtcantly lower temperature.

According to another feature of this invention gas-entrained calcined lime dust from the calcining bed is passed directly through the fiuidized mass of uncalcined limestone solids in a preheating bed while in the presence of carbon dioxide gas and yet undesirable carbonation of the lime dust is avoided. This is accomplished by maintaining the fiuidized mass of limestone solids at a temperature discouraging or inhibiting to lime carbonation; that is, at a temperature that favors limestone decomposition rather than lime carbonation or at a temperature Whereby neither decomposition nor carbonation is favored; in short, a lime-carbonation discouraging temperature. Both of the foregong features are interrelated, that is, the substantially constant preheating temperature is automatically maintained within a temperature range that discourages lime carbonation. This is especially important when calcining decrepitating limestone under solids fiuidizing conditions such as described in U. S. Patent 2,548,642, because under such conditions large quantities of calcined lime dust are formed in the calcining chamber. It is especially advantageous to recover these large quantities of dust in substantially pure form from the entraining gases exiting from the calcining bed.

Before presenting a detailed description of the invention hereof it will be advisable to discuss the general nature and operation of fluidized solids reactors as referred to herein.

In general, in the fluidized solids technique for treating solids, a bed of nely subdivided solids is maintained as a dense mobilized homogeneous suspension behaving like a turbulent liquid and exhibiting a fluid-level. This is accomplished by passing through the bed an uprising stream of gas at a Velocity suicient to expand considerably the depth of the bed as well as to maintain its particles in turbulent suspension in the uprising gas stream, but at a velocity insufiicient to cause the gas to entrain and carry out of the reactor any substantial quantity of solid particles. Under such conditions the bed is called a fiuidized bed. The fluid-level of this fiuidized bed is maintained by the use of a spillpipe or overfiow arrangement so that as more solid particles are introduced into the bed the resulting increased depth causes the particles to overfiow down through the spill-pipe just as a fluid does.

In a reactor having a plurality of zones, several superposed beds are simultaneously maintained in such a fluidized state. Each fluidized bed is usually a separate distinct treatment stage. The treated solid particles from a superjacent bed are discharged or allowed to overow to a suhjacent bed for further treatment then overflowed to the next subjacert bed for even further treatment, etc. This process continues until the particles have passed through all of the fiuidized beds after which they are discharged from the reactor.

Due to the turbulent nature of the uidizecl beds, heat exchange by and among the particles thereof is almost instantaneous so that if two portions of particles, each at a different temperature from the other, are commingled in a fluidized bed the resulting mixture will almost instantly assume a temperature intermediate the temperatures of the portions commingled. Further, this rapid heat exchange creates a substantially uniform temperature throughout the bed.

A reactor having a plurality of superposed fluidized beds is generally employed to calcine finely divided limestone solids in order to produce lime thererom. The fiuidized beds are so arranged that at least two upper beds are preheating beds and at least one intermediate bed is a calcining bed wherein calcining and uel combustion occur, and one or more further subjacent beds are utilized as calcined solids cooling and gas preheating beds. Incoming limestone is preheated in the upper preheating beds by heat transfer from hot gases rising from the calcining bed. Preheated solids are discharged from the preheating beds to the calcining bed where they are further heated by uel combustion within that bed to calcining temperatures, and are calcined therein. calcined lime is discharged to a subjacent cooling bed where it is cooled by heat transfer to uprising uidizing gases thus at the same time preheating the uprising gas The process is made continuous by continuously feeding limestone solids to the uppermost bed, overflowing the solids to the intermediate and lower beds, and finally to discharge. Variations of these processes provide for reactors having several beds for one or more of the separate zones. That is, there may be several calcining and combustion beds as well as a plurality of solids preheating and solids cooling beds.

The best embodiment of the invention now known to us has been selected for the purpose of illustration, but it is to be understood that it is illustrative only and not limiting for obvously changes in arrangement, Construction and detail can be made without departing from the scope of the invention as defined in the appended claims, bearing in mind however that their requirements include equivalents thereof.

In the drawings, Figure 1 is an idealized partial View of a multi-chambered fiuidized solids reactor such as the one shown in Figure 2 and shows the calcining and directly superjacent preheating Zones. Figure 2 is a vertical sectional View of a preferred type of reactor showing this invention in a preferred embodiment.

In Figure 1, zone C is a preheating zone and zone D a calcining zone. Partially preheated limestone solids flow downwardly through downcomer 35 to enter limestone preheating bed 42 which rests upon constriction plate 40 having apertures 4! and is adapted to hold thereon a bed of solids 42 for preheating. Preheated limestone from bed 42 enters downcomer 45 at entrance-way 44 and flows downwardly through downcomer 45 to calcining bed 52 which rests upon constriction plate 50 having apertures El. Bed 52 is maintained at calcining temperatures by supplying fuel thereto through conduits such as 96 and 91 and combusting such fuel within the bed. As the limestone is calcined in bed 52 a considerable quantity of it decrepitates or brezi-ks down into ultra-fine calcined lime particles so that there exists in the bed both coarse and flow downwardlly to'a coolingbed orto discharge. The' ultra-fine particles are entrained i in the uprising fluidizing gas and-areoarried out of bed 52 upwardly through freeboard-space 53 thence through apertures ti of constriction plate 40 into bed 42. The fine particles are then carriedupwardly through bed iz and freeboard-` space 43 finallyleavingthe reactor'via Conduit H, i These entrained lime solids'are carried via Conduit H, to dust-diminishingstation m where the solids are separated fromstheentraining. gas;

The substantiallydust-free gase exitsfrorn dust-' diminishing station -:18-via,conduit 'l3'whi1ethe separatediime solids exit at ?2.

In Figure 2 the total assembly called a reactor R is preferably a vertical-cylinder made up of zones ,such as A, B, C, D and. E suitably secure@ together each havinga metal outer wall !2 and lined with` insulationand firesbrick [3. There actor has a top and a coned bottom !5 pro vided with an outlet lil suitably valved as at H. Zone A is provided with a constriction plate 223 having a plurality of orifices such ,as that one shown at 21; The plate extends across the reactor through -its cross-sectional area `and is adapted to hold' thereona fluidized bed 22 of finely divided limestone solids-being heated by heat transfer, above which is a freeboard space 23.

Zone B has-a similar-const'ction plate 38 with orifices suchas at 3! and is adapted to hold thereon a fluidized bed 32 of such solids-being heated by heat transfer above which: is a freeboard space 33. Zone C has a constriction plate lt with orifices such as at Mana is adapted to hold thereon a fiuidized bed. '42 of such solids being heated by heat transfer above which is a freeboard space 43. 'Zone'D has a constriction plate '52 With orifices suchas ati! and is adapted to hold thereon a fluidized bed 52 of such solids being calcinecl; above which-is a freeboard space' 53. Zone E hasa constriction plate with, oria 'iuidized bed 62 of calcined solids being cooled by heat transfer; above which is a freeboard space- 63. Zones A, -B and C' are'preheating zones, zone-2 fluid-level of bed %win zone C` is controlled by entrance 44. to Conduit or spill-pipe through which solids drop into bed 52 in zone D. The fluid-level of bed 52, in zone D is controlled by dust-free gases aredischarged at 83.

fices such as at El 'and is adapted-to hold thereon 4 Conduit., 92"1WhChfS suitablyrjzvalved as` at' 93; This gaspasses upwardly through the constriction platethenceth'ough bedfiz, thence through freeboardspace 63; thence through constriction plate 5!)` and' -bed- 52; :thence through freeboard space-53, 'thence through constriction plate 40- and bed 42, thence throughzfreeboard space 43' from Whence'-it .is discharged via Conduit 'H to dust-diminishing: station 'III:` In dust-diminish- 'ing station 'lo'entrained-lime dust is sepa'ated from' the gases anduthisxdust is discharged at ?2 whiletthe substantially;dust-free gases are discharged via conduit 13 to .enter the reactor at Minto windbox; :15 below constriction plate 30. The gases ;thenrise-upwardly through constriction plate 30 :and :bed 32,'thence through freeboard spacera and finally through constric tion plate 20, bed 22; freeboard space 23, an-:l finally are discharged' from the reactor via conduit 94' suitably valved as at 95th a further dustdiminishing station so.

In. dust-diminishing station 80fany entrained dust is separatedfromthe discharge gasesand this entrained dust is discharged at 82 while the Fuel to provide heat for 'the: calcination is supplied to bed 52 va suitably valved conduits 96 and t'i. Oxygen tosupport thecombustion oftthis uel is provided inthe' fi-uidizing gaswhich enters 'through conduit 92."

A pipe ss'suitably va-lved and provided with a burner. is provided at'the bottom of the reactor to supply heat -for starting uphowever any type of preheating torchgcan 'bea used; Preheating is used only until the temperature in calcining in the various beds orzones but are' omitted from the drawing to: avoid unnecessarily complioating it.:

In starting up the* reaotorR `hea t is supplied initially through conduit 98 and its attached burner (not shown) whilethe beds are established` and maintained by continuously feedi-ng solids` intobed 22: through` suitablyvalved conduit 9& and the solidsjare allowed to'fiow downwardly through* the overflow conduits as previously described. Fluidizing and combustion sup porting gasesare introduced through pipe When' the reaotor ;is in full and continuous operation zone D is the hottest zone and is where calcination and combustion take place. Here the entrance 54 into Conduit or spill-pipe 55 through V which calcined solids pass to bed 62 in subjacent zone E. The uidrlevel-of bed 52 is controlled by entrance 54 to `Conduit 65 through which oooled calcinecl partioles pass todischarge- A solid partitioning plate is provided in zone B below constriction plate 36 and .extending throughout the cross-sectional area oflthelre actor in order to create a windbox ?Bandto prevent the exit gases rising from bed 42 in zone C from passing directly through constriction plate 35 into bed 32.

Fluidizing gas is supplied to. the reacto' -via temperature must be maintained sufficiently high southat calcination of the limestone solids will take place and the fuel 'supplied through conduits 36 and 9T-Wi11-be substantially oombusted. In zone C'where preheatingconditions are maintained the solids of bed 42 must be kept-within a temperature rangethat is discouraging to lime carbonation. This temperature is lower than the temperature .of i zone D where conbustion and calcination take' place. Solidsin bed 42 are preheated-- bythe `transfer of sensible-heat from the dust-laden hot gases rising -from zone D while the solids* in beds 22 and 32 are preheated by transferof sensibleheat fromthe substantially dust-free hot gasesrisng from windbox ?3:

The diameter of theenclosed uidized becis 22 and azis smaller thanthe diameter of fiuidized beds: 42- and zwhileethe orifices-invplates E@ and 'oareincreasedin number or size or both.-

Thisis to insure thaitz the uprising :gas 'will have 22 and 32. That is, as the gases pass through beds 32 and 42 they lose heat and hence occupy a smaller Volume and their upward velocity is correspondingly decreased. Therefore it is necessary to provide a correspondingly smaller Volume for such gases to pass through in order to maintain them at fluidizing velocities. Similarly the diameter of bed 62 is also smaller than that of beds 42 and 52. This is so because cool fluidizing gas entering through Conduit 92 occupies a relatively small Volume and a decreased bed diameter is required in order to insure fiuidizing Velocities in bed 62.

In some cases it may be necessary to decrease the diameter of bed 32 in order to maintain solids uidization therein, however this will depend upon the particular case and upon the Volume and velocity of the fiuidizing gases used. An alternate method for insuring fiuidization in the upper preheating beds would be to supply additional fluidizing gases to those beds, but this involves additional Operating expense and for this reason the method shown in the drawings is preferred.

By proper design, bed 22 may be operated as a limestone solids sizing bed wherein limestone dust is removed. such a design would provide for a decreased diameter in such bed in order to insure a sufficiently high fluidizing gas velocity to entrain limestone dust and carry it from the bed. such design would further provide for an increase in the number or diameter of orices in order to maintain a reasonable pressure drop through the constriction plate. If such a design is employed then it would be unnecessary to separately remove limestone dust from the limestone solids before such solids are introduced into the reactor.

An alternate design, not shown in the drawings, includes locating the dust-diminisher or cyclone 80 within the freeboard space 43, above bed 42, so that heat loss from the gases due to radiation is kept at a minimum.

Example The operation of an embodiment of this invention will be described in connection with the calcination of finely divided limestone in a commercial fiuidized solids reactor of the type shown in Figure 1 of the drawings.

The reactor employed has an overall height of 45 feet and a maximum inside diameter in the calcining bed of 12 feet. The solids preheating bed directly superjacent to the calcining bed is 12 feet in diameter while the next superjacent preheating bed is 11 feet in diameter and the uppermost bed has a diameter of 10 feet. The lowermost solids-cooling gas-preheating bed has a diameter of 8 feet. It is also to be noted that in addition to changing the bed diameter the number of orifices in the various constriction plates is increased or the size of such orifices is increased so as to allow free passage of the uprising gases. Bed depths are maintained as foilows: preheating beds, 2 feet; calcining bed, 5 feet; and solids cooling bed, 2 feet. Heighth of reeboard spaces above the beds is as ollows: above uppermost bed, 4' 6" above next two subjacent beds, 3' 6"; above calcining bed, 5 feet; and above cooling bed, 3' 6".

Fluiding gas enters through Conduit 92 in suffcient quantity and under sufficient pressure so that it has an upward velocity through the reactor of approximately 2 feet per second. This velocity is computed without reference to the solids present in the reactor; that is, the 2 feet per second is the upward velocity which the gas would have if there were no solids in the reactor. This velocity is referred to as space rate. Due to Volume changes in the gas as it passes through the reactor, the space rate is maintained substantially constant throughout the reactor.

solids to be treated are introduced into the to of the reactor and flow successively downwardly through the beds so that cooled calcined solids are discharged from the bottom of the reactor. In this case the solids are pre-Classified to remove a major portion of the limestone dust before introducing such solids into the reactor. Any remaining dust is either passed downwardly through the reactor for calcination therein or is blown from the reactor by the gases exiting :from the uppermost bed. Gases exiting from the top of the reactor are discharged to a cyclone for separation of any remaining entrained dust.

Liquid fuel is injected into the calcining bed and is combusted therein in sufcient quantities to maintain the solids of such bed at calcining temperatures in the range of 1700 to 1950 F. depending upon the product desired. Dust-laden gases exiting from the calcining chamber pass upwardly through the directly superjacent preheating bed and the solids of such bed are automatically maintained in the temperature range of 1500 to l600 F. As solids are calcined in the calcining bed a considerable quantity of them decrepitate or break down forming lime dust. A large quantity of this dust is entrained in the uprising fiuidizing gas and is carried from the calcining bed upwardly through the directly superjacent limestone preheating bed thence to a cyclone where the entrained lime dust is recovered in substantially pure form. The dustfree gases are discharged from the cyclone for further use in the remaining preheating beds.

When in normal operation fiuidizing gas is supplied to the bottom of the reactor at a rate of approximately 3300 C. F. M. (measured at F. and one atmosphere of pressure). Depending upon the temperature maintained in the calcining bed, which may lie in the range from 1700 to 1950 F., relative conditions existing in the calcining bed and directly superjacent preheating bed are as follows:

Temperature Temperature oi gases Volume of gases dis V1umc,9f

dschar d gases leaving gases leav ng i ge from %Mining charged from preheatmg %hmm bed bed, o, FM. bed, o. r. M.

Thus, when the temperature in the caleining bed undergoes a 210 F. change yet the temperature of the preheating bed changes only 25 F.

This reactor has an average production capacity of approximately 107 tons of calcined lime per twenty-four hours. About thirteen tons per twenty-four hours of this product are carried out of the calcining bed as gas-entrained lime dust and passed upwardly through the directly superjacent preheating bed thence to a dust cyclone where it is recovered as substantially pure calcined lime product.

We claim:

1. The process for heat treating finely-divided limestone to yield calcined lime, which comprises the steps of establishing and maintaining within an enclosed chamber three superposed beds of finely-divided solids including an upper and an intermediate solids-preheating bed maintained ,under solids-preheating conditions and a lower solids-calcining bed maintained at limestone salcining temperatures, continuously supplying finely-divided limestone solids into the upper preheating bed, preheating such solids in such bed, transferring such preheated solids to the intermediate preheating bed, further preheating the solids in the intermediate bed and then transferring the further preheated solids to the calcining bed, n'aintaining each such bed as a fiuidized bed wherein its solids are maintained as a dense mobilized homogeneous suspension behaving like a turbulent liquid and exhibting a fluid level by passing upwardly through the calcining bed and thence successively through the intermediate and upper beds an uprising stream of gas at fiuidizing veiocities, calcining solids within the calcining bed to form finelydivided calcine lime solids as well as calcined lime dust dischargng calcined solids from the latter bed, entraining a portion of the lime dust formed in the latter bed in the uprising gases, passing these uprising gases together with entrained lime dust upwardly through the intermediate preheating bed so that they are cooled during passage through said intermediate bed, transferring the resulting cooler gases and entrained lime dust to a dust-diminishing station to separate said dust from said gases, discharging separated lime dust from the latter station,

passing the resulting dust-diminished gas up- Wardly through the upper solids preheating bed, and maintaining the dust-laden gases entering the dust diminishing station at a substantially constant temperature that is significantly lower than the temperature at which such gas leaves the calcining bed and without recarbonation of the entrained lime dust by maintaining the intermediate bed at a temperature discouraging to lime carbonation that is significantly lower than the temperature of said calcining bed.

2. The process according to claim '1 wherein the temperature of the dust-laden gases exiting from the calcining bed is maintained to lie in the range of 1700 F. to 1900 F.

3. The process according to claim 1 wherein the temperature of the dust-laden gases exiting from the limestone solids preheating bed through which such gases pass before entering the dustdiminishing station is maintained to lie in the temperature range of substantially 1500 F. to 1600 F.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,409,707 Roetheli Oct. 22, 1946 2,529,366 Bauer Nov. 7, 1950 2,541,186 Anderson Feb. 13, 1951 2,548,642 White Apr. 10, 1951 

